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US20150180025A1 - Lithium Metal Complex Oxide - Google Patents

Lithium Metal Complex Oxide Download PDF

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Publication number
US20150180025A1
US20150180025A1 US14/413,888 US201314413888A US2015180025A1 US 20150180025 A1 US20150180025 A1 US 20150180025A1 US 201314413888 A US201314413888 A US 201314413888A US 2015180025 A1 US2015180025 A1 US 2015180025A1
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metal complex
complex oxide
lithium metal
powder
lithium
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Tetsuya Mitsumoto
Hitohiko Ide
Shinya Kagei
Yoshimi Hata
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Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Assigned to MITSUI MINING & SMELTING CO., LTD. reassignment MITSUI MINING & SMELTING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HATA, YOSHIMI, KAGEI, SHINYA, MITSUMOTO, TETSUYA, IDE, HITOHIKO
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium metal complex oxide, which can be used as a positive electrode active material of a lithium battery, and which, in particular, can exhibit excellent performance as a positive electrode material of a battery that is mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV).
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • Lithium batteries and among these, lithium secondary batteries, having characteristics such as a large energy density and a long life span, are used widely as power sources for home appliances such as video cameras and portable electronic devices such as notebook computers and mobile phones, and the like. Recently, they have been put into application in large batteries that are mounted on an electric vehicle (EV), a hybrid electric vehicle (HEV) and the like.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • a lithium secondary battery is a secondary battery having a structure in which, during charging, lithium dissolves out from the positive electrode as an ion and moves towards the negative electrode to be intercalated and conversely, during discharging, the lithium ion returns from the negative electrode to the positive electrode, and it is known that the high energy density of the battery is based on the electric potential of the positive electrode material.
  • lithium metal complex oxides such as LiCoO 2 , LiNiO 2 or LiMnO 2 having a layered structure are known in addition to lithium manganese oxides (LiMn 2 O 4 ) having a spinel structure.
  • LiCoO 2 has a layered structure in which a layer of lithium atoms and a layer of cobalt atoms are stacked alternately via a layer of oxygen atoms, and has a large charge-discharge capacity and excellent diffusivity for intercalation and disintercalation of lithium ions. Accordingly, most of the lithium secondary batteries that are commercially available at the present moment have a lithium metal complex oxide like LiCoO 2 with a layered structure.
  • a lithium metal complex oxide with a layered structure like LiCoO 2 and LiNiO 2 is represented by the general formula LiMeO 2 (Me: transition metal).
  • the crystal structure of the lithium metal complex oxide with a layered structure belongs to space group of R-3m (“-” is usually added on upper part of “3” and represents inversion, and the same shall apply for the followings) and Li ion, Me ion, and oxide ion occupy 3a site, 3b site, and 6c site, respectively.
  • the layer consisting of Li ions (Li layer) and the layer consisting of Me ions (Me layer) are stacked alternately via O layer consisting of oxide ions to represent a layered structure.
  • LiNi x Mn 1 ⁇ x O 2 As a lithium metal complex oxide (LiM x O 2 ) with a layered structure, an active material represented by the formula LiNi x Mn 1 ⁇ x O 2 (in the formula, 0.7 ⁇ x ⁇ 0.95) which is obtained by adding an alkali solution to an aqueous mixture solution of manganese and nickel to co-precipitate manganese and nickel, adding lithium hydroxide, and subsequently calcining them has been disclosed in Patent Document 1, for example.
  • Patent Document 2 discloses a positive electrode active material composed of crystal particles of an oxide containing three kinds of transition metals having the layered crystal structure and represented by Li[Li x (A P B Q C R ) 1 ⁇ x ]O 2 (in the formula, A, B and C respectively means different three kinds of transition metal elements, and ⁇ 0.1 ⁇ x ⁇ 0.3, 0.2 ⁇ P ⁇ 0.4, 0.2 ⁇ Q ⁇ 0.4, 0.2 ⁇ R ⁇ 0.4), in which oxygen atom constituting the oxide is arranged for cubic close packing.
  • Patent Document 3 for providing laminar lithium nickel manganese complex oxide powder having a high bulk density, disclosed is a method for producing a laminar lithium nickel manganese complex oxide powder in which a slurry containing at least a lithium source compound, a nickel source compound, and a manganese source compound, which are ground and mixed, in a molar ratio [Ni/Mn] of nickel atom [Ni] to manganese atom [Mn] of 0.7 to 9.0 is dried through spray drying and calcined to prepare laminar lithium nickel manganese complex oxide powder, which is then ground.
  • V vanadium
  • B boron
  • Patent Document 5 for the purpose of providing a positive electrode active material for a nonaqueous secondary battery consisting of primary particles which can maintain high bulk density or battery characteristics and has no problem of having a crack, disclosed is a positive electrode active material for a nonaqueous secondary battery which is a powdered lithium complex oxide of monodisperse primary particles with lithium and one kind of element selected from a group of Co, Ni, and Mn as main components with D50 of 3 to 12 ⁇ m, a specific surface area of 0.2 to 1.0 m 2 /g, a bulk density of 2.1 g/cm 3 or more, and having characteristics of not showing an inflection point of a volume decrease rate by a Cooper Plot method up to 3 ton/cm 2 .
  • Patent Document 6 relates to powder of lithium metal complex oxide represented by the formula: Li z Ni 1 ⁇ w M w O 2 (provided that, M is at least one metal element selected from the group consisting of Co, Al, Mg, Mn, Ti, Fe, Cu, Zn and Ga, and the relationships 0 ⁇ w ⁇ 25 and 1.0 ⁇ z ⁇ 1.1 are satisfied), and it discloses a positive electrode active material for a nonaqueous electrolyte secondary battery characterized in that it is composed of primary particles of the lithium metal complex oxide powder and secondary particles formed of a group of plural primary particles in which the shape of the secondary particles are spherical or oval sphere shaped, 95% or more of the secondary particles has a particle diameter of 20 ⁇ m or less, an average particle diameter of the secondary particles is 7 to 13 ⁇ m, a tap density of the powder is 2.2 g/cm 3 or more, an average volume of a pore with an average diameter of 40 nm or less in measurement of a pore size distribution by a nitrogen adsorption method
  • Patent Document 7 discloses lithium transition metal oxide having a layered structure obtained by grinding with, for example, a wet type grinder or the like until D50 becomes 2 ⁇ m or less and performing drying with granulation and calcining by using a heat spray dryer, characterized in that a ratio of the crystallite diameter relative to the average powder particle diameter (D50) as measured by a laser diffraction scattering particle size distribution measurement method is 0.05 to 0.20.
  • Patent Document 8 suggests, for preventing a decrease in battery performance as the lithium-containing complex oxide as an electrode material is affected by moisture, to form a coating film consisting of a water-repellent material such as a silane coupling agent on at least one of the surface of lithium-containing complex oxide microparticles and the surface of the positive electrode.
  • a water-repellent material such as a silane coupling agent
  • Patent Document 1 JP H8-171910 A
  • Patent Document 2 JP 2003-17052 A
  • Patent Document 3 JP 2003-34536 A
  • Patent Document 4 JP 2004-253169 A
  • Patent Document 5 JP 2004-355824 A
  • Patent Document 6 JP 2007-257985 A
  • Patent Document 7 JP 4213768 B1 (WO 2008/091028)
  • Patent Document 8 JP H11-224664 A
  • the lithium metal complex oxide is generally admixed with a conductive material and a binder material consisting of a binder or the like to produce a positive electrode mixture in a slurry state, which is then coated on a conductor for producing a positive electrode.
  • the particle size of the lithium metal complex oxide is excessively large, particles are precipitated during storage of the slurry, yielding an non-uniformity state.
  • the lithium metal complex oxide preferably has a small particle size, specifically D50 of less than 10 ⁇ m.
  • the lithium metal complex oxide has a particle size (D50) of less than 10 ⁇ m, particles of the lithium metal complex oxide aggregate to each other in the slurry to yield lower viscosity stability of slurry during storage of the slurry, and thus the property of coating a current-collecting foil is deteriorated, or due to aggregation of the lithium metal complex oxide (active material), a contact with the conductive material is weakened so that charging and discharging of the active material becomes difficult. As a result, a problem like reduced discharge capacity during high temperature cycles occurs.
  • D50 particle size
  • the present invention which relates to a lithium metal complex oxide used for a positive electrode of a lithium battery, is to provide a novel lithium metal complex oxide powder which is capable of maintaining stability of the slurry viscosity during storage of a slurry even if the particle size (D50) is less than 10 ⁇ m, and which is also capable of suppressing a decrease in the discharge capacity during high temperature cycles.
  • the present invention suggests a lithium metal complex oxide characterized by having D50, which is based on a volume-based particle size distribution as obtained by a laser diffraction scattering particle size distribution measurement method (referred to as “D50”), of less than 10 ⁇ m and a carbon amount per unit BET specific surface area of from 1100 ppm/(m 2 /g) to 7500 ppm/(m 2 /g).
  • D50 laser diffraction scattering particle size distribution measurement method
  • the lithium metal complex oxide suggested by the present invention has high affinity to a solvent and excellent dispersability in a slurry, it allows production of an electrode having evenly dispersed active materials, and as a result, it enables an improvement of capacity retention rate during high temperature cycles compared to a product of a related art.
  • FIG. 1 is a diagram for describing the constitution of a cell for electrochemical evaluation, which is produced for the evaluation of battery characteristics of Examples.
  • the lithium metal complex oxide of this embodiment indicates powder having particles of lithium metal complex oxide as a main component (hereinbelow, referred to as “particles of the present lithium metal complex oxide”), in which the lithium metal complex oxide has D50 of less than 10 ⁇ m and has a layer containing carbon on a part or the whole of the surface of a particle.
  • a main component implies the meaning of allowing other constituents to be contained to such an extent that the functions of the main constituent are not prevented.
  • the content ratio of the main component cases in which it occupies 50% by mass or more, particularly 70% by mass or more, of which 90% by mass or more, of which 95% by mass or more (including 100%) of the present lithium metal complex oxide are included.
  • the present lithium metal complex oxide may contain, as impurities, SO 4 in an amount of 1.0% by mass or less and other elements in an amount of 0.5% by mass or less for each. This is because it is believed that such amount hardly has any influence on the characteristics of the lithium metal complex oxide.
  • the particles of the present lithium metal complex oxide can be either a lithium metal complex oxide with a layered structure or a spinel type (Fd3-m) lithium metal complex oxide. Since the effect of the present invention is mainly based on the influence by a surface layer of particles, it is believed that any of those lithium metal complex oxides can exert the effect.
  • the particles of lithium metal complex oxide with a layered structure mean the particles of lithium metal complex oxide having a layered structure in which a layer of lithium atoms and a layer of transition metal atoms are stacked alternately via a layer of oxygen atoms.
  • “1+x” is 1.00 to 1.07, preferably 1.01 or more or 1.07 or less, and more preferably 1.02 to 1.06.
  • M is any one or more kinds of Mn, Co, Ni, a transition element present between the elements of Group 3 and the elements of Group 11 of the periodic table, and a typical element up to Period 3 of the periodic table.
  • examples of the transition element present between the elements of Group 3 and the elements of Group 11 of the periodic table and the typical element up to Period 3 of the periodic table include Al, V, Fe, Ti, Mg, Cr, Ga, In, Cu, Zn, Nb, Zr, Mo, W, Ta, and Re.
  • M can be any one or more kinds of Mn, Co, Ni, Al, V, Fe, Ti, Mg, Cr, Ga, In, Cu, Zn, Nb, Zr, Mo, W, Ta and Re, and it can be also composed only of three kinds of the elements, that is, Mn, Co and Ni, or may contain one or more kinds of other elements in addition to those three elements. It may also have other constitution.
  • value of ⁇ be 0.10 to 0.45, of which 0.15 to 0.40, and in particular 0.20 to 0.35 is more preferable.
  • value of ⁇ be 0.05 to 0.40, of which 0.05 to 0.30, and in particular 0.05 to 0.25 is more preferable.
  • value of ⁇ be 0.30 to 0.75, of which 0.40 to 0.70, and in particular 0.45 to 0.65 is more preferable.
  • One of the characteristics of the powder of the present lithium metal complex oxide is that D50 based on a volume-based particle size distribution as obtained by a laser diffraction scattering particle size distribution measurement method is less than 10 ⁇ m.
  • D50 of the powder of the present lithium metal complex oxide is less than 10 ⁇ m, non-uniformity caused by precipitation of the particles during storage of a slurry can be prevented.
  • D50 of the powder of the present lithium metal complex oxide be 8 ⁇ m or less, of which 7 ⁇ m or less, and in particular 4 ⁇ m or less is more preferable.
  • D50 of the powder of the present lithium metal complex oxide be 0.5 ⁇ m or more, and of which 1 ⁇ m or more is particularly preferable.
  • D50 adjustment be carried out based on adjustment of D50 of starting materials, adjustment of temperature or time for calcination, or adjustment of D50 by comminuting after the calcination.
  • adjustment methods are not limited thereto.
  • the present lithium metal complex oxide preferably has a surface layer containing carbon on the whole or a part of the surface of a particle.
  • the surface layer can be formed by a surface treatment using a coupling treatment agent.
  • a coupling treatment agent for example, when a surface layer is formed by a surface treatment using a silane coupling agent, the surface layer contains oxygen, silicon, and carbon.
  • a surface layer is formed by a surface treatment using a titanium coupling agent, the surface layer contains oxygen, titanium, and carbon.
  • a surface layer is formed by a surface treatment using an aluminum coupling agent, the surface layer contains oxygen, aluminum, and carbon.
  • the surface layer may be present such that it can coat the whole surface of the particle of the present lithium metal complex oxide. Alternatively, it may be present partially on the surface such that there is a portion in which the surface is not present. Actually, partial presence of the surface layer on a surface of the particle of the present lithium metal complex oxide to allow direct contact between exposed particle surface and an electrolyte solution is preferred from the viewpoint of suppressing an increase of electric resistance on the particle surface.
  • the present lithium metal complex oxide have a carbon amount per unit BET specific surface area of from 1100 ppm/(m 2 /g) to 7500 ppm/(m 2 /g), of which 1100 ppm/(m 2 /g) to 5000 ppm/(m 2 /g), and particularly 1100 ppm/(m 2 /g) to 3000 ppm/(m 2 /g) is more preferable.
  • the lithium metal complex oxide even when the particle size (D50) is less than 10 ⁇ m, by attaching organic substances to a surface of the particles and having a carbon amount per unit BET specific surface area of from 1100 ppm/(m 2 /g) or more, an increase in slurry viscosity can be suppressed. Accordingly, hysteresis can be suppressed during the evaluation of a slurry and also a decrease in discharge capacity during high temperature cycles can be suppressed.
  • the amount of the organic substances attached thereto is excessively high, electric resistance may occur on a surface of the particles during charging and discharging. From this point of view, it is preferably 7500 ppm/(m 2 /g) or less, of which 5000 ppm/(m 2 /g) or less, and particularly 3000 ppm/(m 2 /g) or less is more preferable.
  • a surface treatment using a suitable amount of a coupling agent may be carried out for the lithium metal complex oxide obtained by comminuting or grinding after calcination.
  • the minimum value of the crushing strength of powder, which is obtained by crushing powder using a micro crushing tester, of the powder of the present lithium metal complex oxide is preferably more than 70 MPa.
  • the minimum value of the crushing strength of the powder of the present lithium metal complex oxide is more than 70 MPa, disintegration of the particles can be suppressed even when it is used as a positive electrode material of a lithium secondary battery and expansion and contraction of the positive electrode material occur during charging and discharging of the lithium secondary battery. As a result, the capacity retention rate, particularly during high temperature cycles, can be further enhanced.
  • the minimum value of the crushing strength of the powder of the present lithium metal complex oxide be more than 70 MPa, of which more than 75 MPa, in particular more than 80 MPa, and even in particular more than 85 MPa is more preferable.
  • the minimum value of the crushing strength of the powder of the present lithium metal complex oxide can be adjusted to a value more than 70 MPa by reducing the size of D50 based on stronger comminuting after calcination or heat treatment compared to a conventional technique.
  • the temperature for calcination is lowered, the average particle diameter of primary particles of co-precipitated powder is reduced, calcination under atmosphere of carbon dioxide is performed to make the average particle diameter of primary particles small, whereby the minimum value of the crushing strength of the powder can be adjusted to a value more than 70 Mpa.
  • the powder of the present lithium metal complex oxide can be obtained as follows, for example.
  • Raw materials like a lithium salt compound, a manganese salt compound, a nickel salt compound, and a cobalt salt compound are weighed, admixed with one another, and ground by using a wet type grinder or the like followed by granulation, calcination, and as necessary, a heat treatment. Then, they are comminuted under desirable conditions, and as necessary, subjected to classification, and then surface-treated by using a coupling agent or the like.
  • lithium salt compound as a raw material examples include lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), LiOH.H 2 O, lithium oxide (Li 2 O), and other lithium fatty acid and lithium halide.
  • hydroxide salt, carbonate salt, and nitrate salt of lithium are preferable.
  • the type of the manganese salt compound is not particularly limited. Examples thereof which may be used include manganese carbonate, manganese nitrate, manganese chloride, and manganese dioxide. Among them, manganese carbonate and manganese dioxide are preferable. Among them, electrolytic manganese dioxide obtained by an electrolytic method is particularly preferable.
  • the type of the nickel salt compound is not particularly limited. Examples thereof which may be used include nickel carbonate, nickel nitrate, nickel chloride, nickel oxyhydroxide, nickel hydroxide, and nickel oxide. Among them, nickel carbonate, nickel hydroxide, and nickel oxide are preferable.
  • the type of the cobalt salt compound is not particularly limited. Examples thereof which may be used include basic cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxyhydroxide, cobalt hydroxide, and cobalt oxide. Among them, basic cobalt carbonate, cobalt hydroxide, cobalt oxide, and cobalt oxyhydroxide are preferable.
  • Mixing of the raw materials is preferably performed by adding a liquid medium like water or a dispersing agent and performing wet mixing to yield a slurry.
  • a liquid medium like water or a dispersing agent
  • wet mixing it is preferable that the slurry obtained be ground by using a wet type grinder.
  • dry type grinding is also employed.
  • the granulation method may be either wet or dry granulation method, or may be extrusion granulation method, tumbling granulation method, fluidized bed granulation method, mixing granulation method, spray drying granulation method, compression molding granulation method, or flake granulation method using a roll or the like.
  • wet granulation is performed, drying thoroughly prior to calcination is necessary.
  • the drying methods it is sufficient that the drying is performed by a well-known method such as spray heat drying method, hot air drying method, vacuum drying method and freeze-drying method, among which the spray heat drying method is desirable. It is desirable to perform the spray heat drying method using a heat spray dryer (spray dryer) (in the present specification, it is referred to as a “spray drying method”).
  • co-precipitated powder to be provided to calcination (in the present specification, it is referred to as a “co-precipitation method”).
  • co-precipitation method co-precipitated powder can be obtained by dissolving raw materials in a solution and precipitating them by controlling conditions like pH.
  • the comminution strength be increased compared to the comminution method of a related art, for example, a comminution method using a rough grinder having the revolution number of 1000 rpm or so.
  • a comminution method using a rough grinder having the revolution number of 1000 rpm or so for example, by reducing D50 based on increased comminution strength by comminuting using a high speed rotary grinder or the like, it is preferably adjusted to be in the range defined by the present invention.
  • the primary particles tend to be large. Accordingly, for a case of employing the co-precipitation method, it is preferable that the calcination temperature be lowered, calcination time be shortened, or primary particle size of the co-precipitated powder be reduced compared to a common co-precipitation method of a related art, or calcination be performed under carbon dioxide atmosphere or the like so that the average particle diameter of the primary particles is reduced and adjusted to be in the range defined by the present invention.
  • calcination be carried out in a calcination furnace under air atmosphere, under oxygen gas atmosphere, under an atmosphere with the oxygen partial pressure adjusted, or under carbon dioxide gas atmosphere, or under other atmosphere, with calcination conditions in which a temperature of higher than 800° C. but lower than 1000° C. (: meaning the temperature when a thermocouple is brought into contact with the calcination object inside the calcination furnace), preferably 810 to 1000° C., and more preferably 810 to 950° C. for 0.5 to 30 hours is maintained.
  • the calcination conditions are preferably selected such that the transition metals are present as solid-solution at an atomic level to exhibit a single phase.
  • calcination furnace There is no particular limitation on the type of calcination furnace.
  • a rotary kiln, a stationary furnace and other calcination furnaces can be used to perform calcination.
  • the heat treatment after the calcination is preferably performed when adjustment of a crystal structure is needed.
  • the heat treatment may be performed under an oxidizing atmosphere like under air atmosphere, under oxygen gas atmosphere, under an atmosphere with the oxygen partial pressure adjusted, or the like.
  • Crushing after calcination or heat treatment is preferably performed by crushing using a high speed rotary grinder as described above.
  • a high speed rotary grinder When crushing is performed by using a high speed rotary grinder, aggregated particles or weakly calcined portions can be crushed and also an occurrence of a deformation of the particles can be suppressed.
  • it is not limited to a high speed rotary grinder.
  • Examples of the high speed rotary grinder include a pin mill.
  • a pin mill is known as a rotary disc type grinder and it is a crusher with a working mode in which negative internal pressure is created according to rotation of a rotary disc attached with pins and powder is suctioned in from an inlet for raw materials. Accordingly, fine particles having small weight are easily carried by air flow and pass through a clearance within a pin mill. On the other hand, coarse particles are certainly crushed. For such reasons, not only the aggregated particles or weakly calcined portions can be certainly crushed but also an occurrence of a deformation of the particles can be suppressed using a pin mill.
  • the revolution number of the high speed rotary grinder is 4000 rpm or more, preferably 5000 to 12000 rpm, and more preferably 7000 to 10000 rpm.
  • Classification after calcination has a technical meaning of particle size distribution adjustment of cohesive powders and also removal of impurities.
  • classification is preferably carried out by selecting a sieve with a desired size.
  • the surface treatment after calcination is preferably performed by a surface treatment of the lithium metal complex oxide by using a coupling agent, or the like.
  • the silane coupling agent as an example of a coupling agent is an organosilicon compound having an organic functional group and a hydrolyzable group in the molecule.
  • those containing an organosilicon compound which has an amino group in the side chain are preferable. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, decyltrimethoxysilane, and glycidoxypropyltrimethoxysilane.
  • aluminate-based coupling agent or a titanate-based coupling agent other than the silane coupling agent it is also possible to use an aluminate-based coupling agent or a titanate-based coupling agent other than the silane coupling agent.
  • the temperature is preferably set to 40 to 200° C.
  • the ratio of an addition amount of a solvent (mass) relative to the mass of the coupling agent is 0.1 to 10, of which 0.1 to 5, and particularly 0.1 to 3 is preferable.
  • the addition amount of a solvent (mass) relative to the mass of the coupling agent is 0.1 to 10, not only the surface coating rate can be easily adjusted but also the solvent can be easily evaporated, and thus preferable.
  • the powder of the present lithium metal complex oxide can be used effectively as a positive electrode active material of a lithium battery.
  • a positive electrode mixture in slurry state can be prepared by mixing the powder of the present lithium metal complex oxide, a conducting material consisting of carbon black or the like and a binder consisting of Teflon (registered trade mark of DuPont, USA) binder or the like. Then, such a positive electrode mixture can be used for the positive electrode, lithium or a material capable of intercalating and disintercalating lithium, such as carbon, can be used for the negative electrode, and a lithium salt such as lithium hexafluophosphate (LiPF 6 ) dissolved in a mixed solvent such as ethylenecarbonate-dimethylcarbonate can be used for the non-aqueous electrolyte to construct a lithium secondary battery.
  • a battery is not limited to such a constitution.
  • a lithium battery having the powder of the present lithium metal complex oxide as a positive electrode active material can exhibit excellent life characteristics (cycle characteristics) when used for charging and discharging repeatedly, and thus it is particularly excellent for applications in positive electrode active material of a lithium battery which is used as a power source to drive motors mounted in an electric vehicle (EV) or a hybrid electric vehicle (HEV).
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • hybrid vehicle means a vehicle that combines the use of two power sources, that is, an electric motor and an internal combustion engine.
  • lithium battery is meant to include all batteries containing lithium or lithium ion inside the battery, such as a lithium primary battery, a lithium secondary battery, a lithium ion secondary battery, or a lithium polymer battery.
  • X or more (X is any number) or “Y or less” (Y is any number) also includes the meaning of “more than X is preferable” or “less than Y is preferable”.
  • Ammonium salt of polycarboxylic acid (SN DISPERSANT 5468, manufactured by San Nopco Limited) was added as a dispersant to ion exchange water such that it corresponds to 6% by mass of the solid content in the slurry and the dispersant was fully dissolved and mixed in ion exchange water.
  • the obtained ground slurry was granulated and dried using a heat spray dryer (spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.). In so doing, granulation-drying was carried out using a rotary disc for spraying, at the revolution number of 24,000 rpm, a slurry supply amount of 3 kg/hr, and a drying tower exit temperature adjusted to 100° C.
  • a heat spray dryer spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.
  • the obtained granulated powder was subjected to temporary calcination at 450° C. in air by using a stationary electric furnace. Subsequently, powder obtained after temporary calcination was calcined at 910° C. for 20 hours by using a stationary electric furnace.
  • the calcined mass obtained after calcination was added to a mortar and crushed using a pestle. It was sifted through a sieve with a mesh size of 5 mm and those passed through the sieve were crushed by using a high speed rotary grinder (pin mill, manufactured by Makino Mfg. Co., Ltd.) (condition for crushing: revolution number of 10000 rpm) followed by classification using a sieve with a mesh size of 53 ⁇ m. Then, the powder of lithium metal complex oxide passed through the sieve was collected.
  • a high speed rotary grinder pin mill, manufactured by Makino Mfg. Co., Ltd.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 1, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 1 and 99 parts by mass of the powder of lithium metal complex oxide, 1 part by mass of n-octyl trimethoxysilane as a surface treatment agent, and 1 part by mass of methanol as a solvent were used and admixed with one another.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 1, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 1 and 97 parts by mass of the powder of lithium metal complex oxide, 2 parts by mass of n-octyl trimethoxysilane as a surface treatment agent, and 1 part by mass of methanol as a solvent were used and admixed with one another.
  • Ammonium salt of polycarboxylic acid (SN DISPERSANT 5468, manufactured by San Nopco Limited) was added as a dispersant to ion exchange water such that it corresponds to 6% by mass of the solid content in the slurry and the dispersant was fully dissolved and mixed in ion exchange water.
  • the obtained ground slurry was granulated and dried using a heat spray dryer (spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.). In so doing, granulation-drying was carried out using a rotary disc for spraying, at the revolution number of 24,000 rpm, a slurry supply amount of 3 kg/hr, and a drying tower exit temperature adjusted to 100° C.
  • a heat spray dryer spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.
  • the obtained granulated powder was subjected to temporary calcination at 450° C. in air by using a stationary electric furnace. Subsequently, powder obtained after temporary calcination was calcined at 910° C. for 20 hours by using a stationary electric furnace.
  • the calcined mass obtained after calcination was added to a mortar and crushed using a pestle. It was sifted through a sieve with a mesh size of 53 ⁇ m. Then, the powder of lithium metal complex oxide passed through the sieve was collected.
  • the collected complex oxide powder was ground by using a collision type grinder having a classifying device (counted jet mill “100AFG/50ATP”, manufactured by Hosokawa Micron Corporation) at conditions including revolution number of rotor for classification: 14900 rpm, air pressure for grinding: 0.6 MPa, grinder nozzle ⁇ : 2.5, three nozzles were used, and supply amount of powder: 4.5 kg/h to obtain powder of lithium metal complex oxide.
  • a collision type grinder having a classifying device (counted jet mill “100AFG/50ATP”, manufactured by Hosokawa Micron Corporation) at conditions including revolution number of rotor for classification: 14900 rpm, air pressure for grinding: 0.6 MPa, grinder nozzle ⁇ : 2.5, three nozzles were used, and supply amount of powder: 4.5 kg/h to obtain powder of lithium metal complex oxide.
  • Example 4 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 4, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 4 and 98 parts by mass of the powder of lithium metal complex oxide, 1 part by mass of n-octyl trimethoxysilane as a surface treatment agent, and 1 part by mass of methanol as a solvent were used and admixed with one another.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 4, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 4 and 97 parts by mass of the powder of lithium metal complex oxide, 2 parts by mass of n-octyl trimethoxysilane as a surface treatment agent, and 1 part by mass of methanol as a solvent were used and admixed with one another.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 4, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 4 and 98 parts by mass of the powder of lithium metal complex oxide, 1 part by mass of 3-glycidoxypropyl trimethoxysilane as a surface treatment agent, and 1 part by mass of methanol as a solvent were used and admixed with one another, and the heat treatment was performed for 1 hour at 100° C. in air.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 4, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 4, 94 parts by mass of the powder of lithium metal complex oxide, 3 parts by mass of 3-glycidoxypropyl trimethoxysilane as a surface treatment agent, and 3 parts by mass of methanol as a solvent were used and admixed with one another, and the heat treatment was performed for 1 hour at 100° C. in air.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 4, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 4, 90 parts by mass of the powder of lithium metal complex oxide, 5 parts by mass of 3-glycidoxypropyl trimethoxysilane as a surface treatment agent, and 5 parts by mass of methanol as a solvent were used and admixed with one another, and the heat treatment was performed for 1 hour at 100° C. in air.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 1, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 1, 98 parts by mass of the powder of lithium metal complex oxide, 1 part by mass of aluminate-containing coupling agent (PLENACT (registered mark) AL-M, manufactured by Ajinomoto Fine-Techno Co., Inc.) as a surface treatment agent, and 1 part by mass of isopropyl alcohol as a solvent were used and admixed with one another, and the heat treatment was performed for 1 hour at 100° C. in air.
  • aluminate-containing coupling agent PANACT (registered mark) AL-M, manufactured by Ajinomoto Fine-Techno Co., Inc.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 1, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 1, 98 parts by mass of the powder of lithium metal complex oxide, 1 part by mass of titanate-containing coupling agent (PLENACT KR-46B, manufactured by Ajinomoto Fine-Techno Co., Inc.) as a surface treatment agent, and 1 part by mass of isopropyl alcohol as a solvent were used and admixed with one another, and the heat treatment was performed for 1 hour at 100° C. in air.
  • titanate-containing coupling agent PANACT KR-46B, manufactured by Ajinomoto Fine-Techno Co., Inc.
  • Example 2 Surface-treated powder of lithium metal complex oxide (sample) was prepared in the same manner as in Example 1, except that powder of lithium metal complex oxide was prepared in the same manner as in Example 1, 98 parts by mass of the powder of lithium metal complex oxide, 1 part by mass of 3-glycidoxypropyl trimethoxysilane as a surface treatment agent, and 1 part by mass of methanol as a solvent were used and admixed with one another, and the heat treatment was performed for 1 hour at 100° C. in air.
  • Ammonium salt of polycarboxylic acid (SN DISPERSANT 5468, manufactured by San Nopco Limited) was added as a dispersant to ion exchange water such that it corresponds to 6% by mass of the solid content in the slurry and the dispersant was fully dissolved and mixed in ion exchange water.
  • the obtained ground slurry was granulated and dried using a heat spray dryer (spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.). In so doing, granulation-drying was carried out using a rotary disc for spraying, at the revolution number of 24,000 rpm, a slurry supply amount of 3 kg/hr, and a drying tower exit temperature adjusted to 100° C.
  • a heat spray dryer spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.
  • the obtained granulated powder was subjected to temporary calcination at 450° C. in air by using a stationary electric furnace. Subsequently, powder obtained after temporary calcination was calcined at 910° C. for 20 hours by using a stationary electric furnace.
  • the calcined mass obtained after calcination was added to a mortar and crushed using a pestle. It was sifted through a sieve with a mesh size of 5 mm and those passed through the sieve were crushed by using a high speed rotary grinder (pin mill, manufactured by Makino Mfg. Co., Ltd.) (condition for crushing: revolution number of 10000 rpm) followed by classification using a sieve with a mesh size of 53 ⁇ m. Then, the powder of lithium metal complex oxide (sample) passed through the sieve was collected.
  • Ammonium salt of polycarboxylic acid (SN DISPERSANT 5468, manufactured by San Nopco Limited) was added as a dispersant to ion exchange water such that it corresponds to 6% by mass of the solid content in the slurry and the dispersant was fully dissolved and mixed in ion exchange water.
  • the obtained ground slurry was granulated and dried using a heat spray dryer (spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.). In so doing, granulation-drying was carried out using a rotary disc for spraying, at the revolution number of 24,000 rpm, a slurry supply amount of 3 kg/hr, and a drying tower exit temperature adjusted to 100° C.
  • a heat spray dryer spray dryer i-8, manufactured by Ohkawara Kakohki Co., Ltd.
  • the obtained granulated powder was subjected to temporary calcination at 450° C. in air by using a stationary electric furnace. Subsequently, powder obtained after temporary calcination was calcined at 910° C. for 20 hours by using a stationary electric furnace.
  • the calcined mass obtained after calcination was added to a mortar and crushed using a pestle. It was sifted through a sieve with a mesh size of 53 ⁇ m. Then, the powder of lithium metal complex oxide passed through the sieve was collected.
  • the collected complex oxide powder was ground by using a collision type grinder having a classifying device (counted jet mill “100AFG/50ATP”, manufactured by Hosokawa Micron Corporation) at conditions including revolution number of rotor for classification: 14900 rpm, air pressure for grinding: 0.6 MPa, grinder nozzle ⁇ : 2.5, three nozzles were used, and supply amount of powder: 4.5 kg/h to obtain powder of lithium metal complex oxide (sample).
  • a collision type grinder having a classifying device (counted jet mill “100AFG/50ATP”, manufactured by Hosokawa Micron Corporation) at conditions including revolution number of rotor for classification: 14900 rpm, air pressure for grinding: 0.6 MPa, grinder nozzle ⁇ : 2.5, three nozzles were used, and supply amount of powder: 4.5 kg/h to obtain powder of lithium metal complex oxide (sample).
  • the content of carbon (C) in the powder of lithium metal complex oxide which has been obtained from each of Examples and Comparative Examples (sample) was measured by using an apparatus for analyzing carbon in solid (EMIA-110, manufactured by HORIBA, Ltd.) with oxygen as carrier gas and a gas pressure of 0.75 ⁇ 0.05 kgf/cm 2 , and standard setting conditions described in the manuals for EMIA-110. Meanwhile, for a sample at high concentration, the sample amount was suitably reduced so as not to have scale over.
  • EMIA-110 manufactured by HORIBA, Ltd.
  • sample which has been obtained from each of Examples and Comparative Examples
  • 0.5 g of sample (powder) was weighed in a glass cell for MONOSORB LOOP (manufactured by Yuasa Ionics Inc., product name “MS-18”), a specific surface area measurement device by the flow gas adsorption method, the inside of the glass cell was replaced with nitrogen gas for 5 minutes with a gas amount of 30 mL/min using a pretreatment device for the MONOSORB LOOP, and then the heat treatment was carried out at 250° C. for 10 minutes in the above nitrogen gas atmosphere. Thereafter, the sample (powder) was measured by the BET one point method using the MONOSORB LOOP.
  • the adsorption gas used during the measurement was a mixture gas of 30% nitrogen:70% helium.
  • the powder of lithium metal complex oxide (sample) which has been obtained from each of Examples and Comparative Examples, using an automatic sample supplier (“Microtorac SDC” manufactured by Nikkiso Co., Ltd.) for a device for laser diffraction particle diameter distribution measurement, the sample (powder) was introduced to a water soluble solvent, and while at a flow rate of 40%, 40 watts ultrasound was applied for 360 seconds. Then, the particle size distribution was measured using a laser diffraction particle size distribution analyzer “MT3000II” manufactured by Nikkiso Co., Ltd. Then, D50 was obtained from the obtained chart of volume-based particle size distribution.
  • the solvent refractive index was 1.36
  • the particle transmitting condition was set at transmitting
  • the particle refractive index was 2.46
  • the shape was non-spherical
  • the measurement range was 0.133 to 704.0 ⁇ m
  • the measurement time was 30 seconds.
  • the mean value from two measurements was used as D50.
  • the powder of lithium metal complex oxide (sample) which has been obtained from each of Examples and Comparative Examples was subjected to measurement of crushing strength (MPa) using a micro crushing tester (manufactured by Shimadzu Corporation), in which ten measurements of the crushing strength were made for each of the secondary particle with D50 ⁇ 2 ⁇ m according to the volume-based particle size distribution. Among the ten measurement values, the minimum value was taken as the minimum crushing strength of particle (MPa).
  • the slurry which has been prepared as described above was evaluated by using the slurry analyzer RheoStress600 (manufactured by Thermo HAAKE). Namely, the slurry was placed between two plates, that is, the top and bottom plates, and the top part was rotated and the revolution number was continuously increased to 1000 [1/s]. Then, the slurry viscosity 1 [Pas] when the shear rate is 100 [1/s] was obtained. Further, the revolution number was continuously reduced to 0 [1/s] and the slurry viscosity 2 [Pas] when the shear rate is 100 [1/s] was obtained. Then, the difference between the slurry viscosity 1 [Pas] and the slurry viscosity 2 [Pas] was measured for each sample, and the resulting value was used as A.
  • the difference in slurry viscosity was also measured in the same manner as above for the slurry which has been stored for 3 days at 25° C. and 30%, and the resulting value was used as B.
  • a paste was prepared by weighing accurately 8.0 g of the powder of lithium metal complex oxide (sample) which has been obtained from each of Examples and Comparative Examples, 1.0 g of acetylene black (manufactured by DENKI KAGAKU KOGYO KABUSHIKI KAISHA) and 8.3 g of a solution containing PVDF (manufactured by Kishida Chemical Co., Ltd.) dissolved at a concentration of 12% by mass in NMP (N-methyl pyrrolidone), adding thereto 5 ml of NMP and mixing thoroughly.
  • NMP N-methyl pyrrolidone
  • This paste was placed on an aluminum foil which serves as a current collector, prepared as a coating film by using an applicator adjusted to a gap of 100 ⁇ m to 280 ⁇ m, vacuum-dried overnight at 140° C., then, punched with 16 mm ⁇ , and compressed by pressing at 4 t/cm 2 to be turned into a positive electrode.
  • the adsorbed moisture was removed by vacuum drying at 120° C. for 120 minutes or longer, and fitted into the battery.
  • the mean value of the weights of the 16 mm ⁇ aluminum foils was determined in advance and the weight of the aluminum foil was subtracted from the weight of the positive electrode to determine the weight of the positive electrode mixture.
  • the content of the positive electrode active material was determined from the mixing ratios of the powder of lithium metal complex oxide (positive electrode active material), acetylene black, and PVDF.
  • the negative electrode was a 19 mm ⁇ 0.5 mm thick metallic Li, and the electrolytic solution used was LiPF 6 dissolved as a solute at 1 mol/L in a solvent of EC and DMC that are admixed with each other at volume ratio of 3:7.
  • TOMCELL registered trade mark
  • TOMCELL which is a cell for electrochemical evaluation, illustrated in FIG. 1 was fabricated.
  • the electrochemical cell after the evaluation of initial charging and discharging efficiency as described above was subjected to a charging and discharging test and the high temperature cycle life characteristics was evaluated by the methods described below.
  • a cell was placed in an environment tester which was set in such a way that the ambient temperature at which the battery is charged and discharged was at 60° C., the cell was prepared so that it could be charged and discharged, left for 4 hours so that the cell temperature reaches the ambient temperature, then, one cycle of charging and discharging was performed with the charging and discharging range of 3.0 V to 4.3 V in which charging uses 0.1 C constant current and constant voltage and discharging uses 0.1 C constant current. Thereafter, the charging and discharging cycle was performed 50 times at 1 C.
  • the percentage (%) of the value determined by dividing the discharge capacity at the 51st cycle by the discharge capacity at the 2nd cycle was obtained as the value for high temperature cycle life characteristics.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Example 8 D50 ⁇ m 7 7 7 2 2 2 2 2 2
  • Carbon ppm 1100 2500 2600 2400 3400 3500 4160 8125 BET m 2 /g 0.8 1.0 0.9 2.1 1.9 1.9 2.0 2.0
  • Carbon ppm/ 1375 2500 2889 1143 1789 1842 2080 4063 amount/BET (m 2 /g) Powder MPa 76 76 77 85 89 91 92 90 crushing strength Change rate % 13 17 29 56 87 70 41 35 of difference in slurry viscosity 60° C.
  • the lithium metal complex oxide having a particle size (D50) of less than 10 ⁇ m
  • the affinity to a solvent can be increased and dispersability in a slurry can be improved.
  • an increase in slurry viscosity can be suppressed and thus hysteresis can be suppressed during the evaluation of a slurry and also a decrease in discharge capacity during high temperature cycles can be suppressed.
  • the amount of the organic substances is excessively high on a particle surface, an increased electric resistance on a surface of the particle may be caused during charging and discharging.
  • the amount of carbon per unit BET specific surface area is preferably 7500 ppm/(m 2 /g) or less.
  • the aforementioned Examples are related to the powder of lithium metal complex oxide with specific composition.
  • the effect of enhancing the viscosity stability during storage of a slurry by defining the particle size and carbon amount per specific surface area is greatly affected by the composition of powder particles.
  • the same effect as Examples is obtained from all of the lithium metal complex oxides regardless of the composition.
  • lithium rich lithium metal complex oxides in which a part of the metal elements constituting the lithium metal complex oxide is replaced with lithium have relatively high pH on a surface of the powder, and thus they have a common problem of easily increasing slurry viscosity.
  • the aforementioned effect is particularly promising for them.

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